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壳聚糖基水凝胶吸附剂的除磷效能及再利用研究
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Abstract:
磷的过量排放会导致水体的富营养化，但其实磷是不可再生资源。若使用可回收且环境友好型的吸附剂吸附去除水中的磷后，将废弃的吸附剂作为植物肥料，或可达到绿色循环再利用的目的。本研究制备了两种壳聚糖基水凝胶球CS-La/Ca和CS-Fe/Ca，考察对比了二者的吸附除磷效果以及吸附磷饱和后P、La、Fe的释放，以探究其作为植物肥料的潜能。CS-La/Ca的磷吸附容量较高(56.22 mg？g？1)，且对不同pH及共存阴离子的适应能力较强，但CS-Fe/Ca的吸附速率比CS-La/Ca快，且吸附饱和后磷的释放量更高，可达2.17 mg？L？1。二者吸附饱和后，功能元素La和Fe的释放量分别为7~20 μg？L？1和30~40 μg？L？1，均为较低水平，不仅不会对植物造成损害，还可作为微量营养元素促进植物生长。因此，CS-La/Ca更适合用作富营养化水体修复材料，而CS-Fe/Ca更适合用作植物肥料，具有循环再利用的潜能。
Excessive discharge of phosphorus can lead to eutrophication of water, but in fact, phosphorus is a non-renewable resource. If recyclable and environmentally friendly adsorbents are used to remove phosphorus from water, the waste adsorbents can be used as plant fertilizers, or the purpose of green recycling can be achieved. In this study, two kinds of chitosan based hydrogel spheres, CS-La/Ca and CS-Fe/Ca, were prepared, and their adsorption and phosphorus removal effects and the release of P, La and Fe after saturated adsorption of phosphorus were investigated and compared, so as to explore their potential as plant fertilizers. CS-La/Ca has a higher phosphorus adsorption capacity (56.22 mg？g？1) and strong adaptability to different pH and co-existing anions, but the adsorption rate of CS-Fe/Ca is faster than that of CS-La/Ca, and the phosphorus release amount after adsorption saturation is higher, reaching 2.17 mgP？L？1. After adsorption and saturation, the release amounts of functional elements La and Fe are 7~20 μg？L？1 and 30~40 μg？L？1, respectively, which are low levels, not only do not cause damage to plants, but also can be used as micronutrients to promote plant growth. Therefore, CS-La/Ca is more suitable for use as eutrophication water restoration materials, while CS-Fe/Ca is more suitable for use as plant fertilizer, which has the potential of recycling.
| [1] | Zhao, Y., Guo, L., Shen, W., An, Q., Xiao, Z., Wang, H., et al. (2020) Function Integrated Chitosan-Based Beads with Throughout Sorption Sites and Inherent Diffusion Network for Efficient Phosphate Removal. Carbohydrate Polymers, 230, Article 115639. https://doi.org/10.1016/j.carbpol.2019.115639 |
| [2] | Yu, J., Zeng, Y., Chen, J., Liao, P., Yang, H. and Yin, C. (2022) Organic Phosphorus Regeneration Enhanced since Eutrophication Occurred in the Sub-Deep Reservoir. Environmental Pollution, 306, Article 119350. https://doi.org/10.1016/j.envpol.2022.119350 |
| [3] | Kong, H., Wang, J., Zhang, G., Shen, F., Li, Q. and Huang, Z. (2023) Synthesis of Three-Dimensional Porous Lanthanum Modified Attapulgite Chitosan Hydrogel Bead for Phosphate Removal: Performance, Mechanism, Cost-Benefit Analysis. Separation and Purification Technology, 320, Article 124098. https://doi.org/10.1016/j.seppur.2023.124098 |
| [4] | Liu, B., Yu, Y., Han, Q., Lou, S., Zhang, L. and Zhang, W. (2020) Fast and Efficient Phosphate Removal on Lanthanum-Chitosan Composite Synthesized by Controlling the Amount of Cross-Linking Agent. International Journal of Biological Macromolecules, 157, 247-258. https://doi.org/10.1016/j.ijbiomac.2020.04.159 |
| [5] | Wang, J., Zhang, G., Qiao, S. and Zhou, J. (2021) Magnetic Fe0/Iron Oxide-Coated Diatomite as a Highly Efficient Adsorbent for Recovering Phosphorus from Water. Chemical Engineering Journal, 412, Article 128696. https://doi.org/10.1016/j.cej.2021.128696 |
| [6] | Karunarathna, M.H.J.S., Hatten, Z.R., Bailey, K.M., Lewis, E.T., Morris, A.L., Kolk, A.R., et al. (2019) Reclaiming Phosphate from Waste Solutions with Fe(III)-Polysaccharide Hydrogel Beads for Photo-Controlled-Release Fertilizer. Journal of Agricultural and Food Chemistry, 67, 12155-12163. https://doi.org/10.1021/acs.jafc.9b02860 |
| [7] | Feng, W., Cui, H., Zhu, H., Shutes, B., Yan, B. and Hou, S. (2023) Layered Double Hydroxides, an Effective Nanomaterial to Remove Phosphorus from Wastewater: Performance, Mechanism, Factors and Reusability. Science of the Total Environment, 884, Article 163757. https://doi.org/10.1016/j.scitotenv.2023.163757 |
| [8] | Qiao, W., Bai, H., Tang, T., Miao, J. and Yang, Q. (2019) Recovery and Utilization of Phosphorus in Wastewater by Magnetic Fe3O4/Zn-Al-Fe-La Layered Double Hydroxides (LDHs). Colloids and Surfaces A: Physicochemical and Engineering Aspects, 577, 118-128. https://doi.org/10.1016/j.colsurfa.2019.05.046 |
| [9] | Ahmed, A.M., Mekonnen, M.L., Jote, B.A., Damte, J.Y., Mengesha, E.T., Lednický, T., et al. (2024) Removal of Phosphate from Wastewater Using Zirconium/Iron Embedded Chitosan/alginate Hydrogel Beads: An Experimental and Computational Perspective. International Journal of Biological Macromolecules, 281, Article 136431. https://doi.org/10.1016/j.ijbiomac.2024.136431 |
| [10] | Beiyuan, J., Wu, X., Ruan, B., Chen, Z., Liu, J., Wang, J., et al. (2024) Highly Efficient Removal of Aqueous Phosphate via Iron-Manganese Fabricated Biochar: Performance and Mechanism. Chemosphere, 364, Article 143207. https://doi.org/10.1016/j.chemosphere.2024.143207 |
| [11] | Liu, S., Fan, F., Ni, Z., Liu, J. and Wang, S. (2023) Sustainable Lanthanum-Attapulgite/Alginate Hydrogels with Enhanced Mechanical Strength for Selective Phosphate Scavenging. Journal of Cleaner Production, 385, Article 135649. https://doi.org/10.1016/j.jclepro.2022.135649 |
| [12] | 王亚, 杨梦, 刘柏, 等. 磁性载镧水凝胶对低浓度磷的吸附性能[J]. 环境工程学报, 2024, 18(10): 2844-2856. |
| [13] | Karasa, J., Ozola-Davidāne, R., Gruškeviča, K., Ozoliņa, K.A., Mikosa, L.I. and Kostjukovs, J. (2024) Phosphorus Removal from Municipal Wastewater Using Calcium/Iron Oxide Composites: Adsorption Efficiency and Impact on Plant Growth. Science of the Total Environment, 955, Article 177227. https://doi.org/10.1016/j.scitotenv.2024.177227 |
| [14] | Santos, A.F., Lopes, D.V., Alvarenga, P., Gando-Ferreira, L.M. and Quina, M.J. (2024) Phosphorus Removal from Urban Wastewater through Adsorption Using Biogenic Calcium Carbonate. Journal of Environmental Management, 351, Article 119875. https://doi.org/10.1016/j.jenvman.2023.119875 |
| [15] | Xu, R., Lyu, T., Zhang, M., Cooper, M. and Pan, G. (2020) Molecular-Level Investigations of Effective Biogenic Phosphorus Adsorption by a Lanthanum/Aluminum-Hydroxide Composite. Science of the Total Environment, 725, Article 138424. https://doi.org/10.1016/j.scitotenv.2020.138424 |
| [16] | Yin, H., Zhang, M., Huo, L. and Yang, P. (2022) Efficient Removal of Phosphorus from Constructed Wetlands Using Solidified Lanthanum/Aluminum Amended Attapulgite/biochar Composite as a Novel Phosphorus Filter. Science of the Total Environment, 833, Article 155233. https://doi.org/10.1016/j.scitotenv.2022.155233 |
| [17] | Zhang, F., Yan, J., Fang, J., Yan, Y., Zhang, S. and Benoit, G. (2023) Sediment Phosphorus Immobilization with the Addition of Calcium/Aluminum and Lanthanum/Calcium/Aluminum Composite Materials under Wide Ranges of Ph and Redox Conditions. Science of the Total Environment, 863, Article 160997. https://doi.org/10.1016/j.scitotenv.2022.160997 |
| [18] | Eltaweil, A.S., Omer, A.M., El-Aqapa, H.G., Gaber, N.M., Attia, N.F., El-Subruiti, G.M., et al. (2021) Chitosan Based Adsorbents for the Removal of Phosphate and Nitrate: A Critical Review. Carbohydrate Polymers, 274, Article 118671. https://doi.org/10.1016/j.carbpol.2021.118671 |
| [19] | Peng, J., Wang, B., Song, Y., Yuan, P. and Liu, Z. (2007) Adsorption and Release of Phosphorus in the Surface Sediment of a Wastewater Stabilization Pond. Ecological Engineering, 31, 92-97. https://doi.org/10.1016/j.ecoleng.2007.06.005 |
| [20] | Johnston, A.E. and Richards, I.R. (2003) Effectiveness of Different Precipitated Phosphates as Phosphorus Sources for Plants. Soil Use and Management, 19, 45-49. https://doi.org/10.1111/j.1475-2743.2003.tb00278.x |
| [21] | Aliyat, F.Z., Maldani, M., El Guilli, M., Nassiri, L. and Ibijbijen, J. (2022) Phosphate-Solubilizing Bacteria Isolated from Phosphate Solid Sludge and Their Ability to Solubilize Three Inorganic Phosphate Forms: Calcium, Iron, and Aluminum Phosphates. Microorganisms, 10, Article 980. https://doi.org/10.3390/microorganisms10050980 |
| [22] | Landa, P. (2021) Positive Effects of Metallic Nanoparticles on Plants: Overview of Involved Mechanisms. Plant Physiology and Biochemistry, 161, 12-24. https://doi.org/10.1016/j.plaphy.2021.01.039 |
| [23] | Zhu, G., Sun, Y., Shakoor, N., Zhao, W., Wang, Q., Wang, Q., et al. (2023) Phosphorus-Based Nanomaterials as a Potential Phosphate Fertilizer for Sustainable Agricultural Development. Plant Physiology and Biochemistry, 205, Article 108172. https://doi.org/10.1016/j.plaphy.2023.108172 |
| [24] | Kirkby, E.A. And Pilbeam, D.J. (1984) Calcium as a Plant Nutrient. Plant, Cell & Environment, 7, 397-405. https://doi.org/10.1111/j.1365-3040.1984.tb01429.x |
| [25] | Márquez-Quiroz, C., De-la-Cruz-Lázaro, E., Osorio-Osorio, R. and Sánchez-Chávez, E. (2015) Biofortification of Cowpea Beans with Iron: Iron’s Influence on Mineral Content and Yield. Journal of Soil Science and Plant Nutrition, 15, 839-847. https://doi.org/10.4067/s0718-95162015005000058 |
| [26] | Huang, G. and Shan, C. (2018) Lanthanum Improves the Antioxidant Capacity in Chloroplast of Tomato Seedlings through Ascorbate-Glutathione Cycle under Salt Stress. Scientia Horticulturae, 232, 264-268. https://doi.org/10.1016/j.scienta.2018.01.025 |
| [27] | Cui, W., Kamran, M., Song, Q., Zuo, B., Jia, Z. and Han, Q. (2019) Lanthanum Chloride Improves Maize Grain Yield by Promoting Photosynthetic Characteristics, Antioxidants Enzymes and Endogenous Hormone at Reproductive Stages. Journal of Rare Earths, 37, 781-790. https://doi.org/10.1016/j.jre.2018.12.006 |
| [28] | Yamamoto, Y. (2018) Aluminum Toxicity in Plant Cells: Mechanisms of Cell Death and Inhibition of Cell Elongation. Soil Science and Plant Nutrition, 65, 41-55. https://doi.org/10.1080/00380768.2018.1553484 |
| [29] | Singh, S., Tripathi, D.K., Singh, S., Sharma, S., Dubey, N.K., Chauhan, D.K., et al. (2017) Toxicity of Aluminium on Various Levels of Plant Cells and Organism: A Review. Environmental and Experimental Botany, 137, 177-193. https://doi.org/10.1016/j.envexpbot.2017.01.005 |
| [30] | Ur Rahman, S., Han, J., Ahmad, M., Ashraf, M.N., Khaliq, M.A., Yousaf, M., et al. (2024) Aluminum Phytotoxicity in Acidic Environments: A Comprehensive Review of Plant Tolerance and Adaptation Strategies. Ecotoxicology and Environmental Safety, 269, Article 115791. https://doi.org/10.1016/j.ecoenv.2023.115791 |
| [31] | Zeng, H., Sun, S., Xu, K., Zhao, W., Hao, R., Zhang, J., et al. (2022) Iron-Loaded Magnetic Alginate-Chitosan Double-Gel Interpenetrated Porous Beads for Phosphate Removal from Water: Preparation, Adsorption Behavior and pH Stability. Reactive and Functional Polymers, 177, Article 105328. https://doi.org/10.1016/j.reactfunctpolym.2022.105328 |
| [32] | Lan, Z., Lin, Y. and Yang, C. (2022) Lanthanum-Iron Incorporated Chitosan Beads for Adsorption of Phosphate and Cadmium from Aqueous Solutions. Chemical Engineering Journal, 448, Article 137519. https://doi.org/10.1016/j.cej.2022.137519 |
| [33] | Zhang, B., Chen, N., Feng, C. and Zhang, Z. (2018) Adsorption for Phosphate by Crosslinked/Non-Crosslinked-Chitosan-Fe(III) Complex Sorbents: Characteristic and Mechanism. Chemical Engineering Journal, 353, 361-372. https://doi.org/10.1016/j.cej.2018.07.092 |
| [34] | Zhu, B., Yuan, R., Wang, S., Chen, H., Zhou, B., Cui, Z., et al. (2024) Iron-Based Materials for Nitrogen and Phosphorus Removal from Wastewater: A Review. Journal of Water Process Engineering, 59, Article 104952. https://doi.org/10.1016/j.jwpe.2024.104952 |
| [35] | He, Q., Zhao, H., Teng, Z., Wang, Y., Li, M. and Hoffmann, M.R. (2022) Phosphate Removal and Recovery by Lanthanum-Based Adsorbents: A Review for Current Advances. Chemosphere, 303, Article 134987. https://doi.org/10.1016/j.chemosphere.2022.134987 |
| [36] | Cui, X., Dai, X., Khan, K.Y., Li, T., Yang, X. and He, Z. (2016) Removal of Phosphate from Aqueous Solution Using Magnesium-Alginate/Chitosan Modified Biochar Microspheres Derived from Thalia Dealbata. Bioresource Technology, 218, 1123-1132. https://doi.org/10.1016/j.biortech.2016.07.072 |
| [37] | 付军, 范芳, 李海宁, 等. 铁锰复合氧化物/壳聚糖珠: 一种环境友好型除磷吸附剂[J]. 环境科学, 2016, 37(12): 4882-4890. |
| [38] | Li, J., Li, B., Yu, W., Huang, H., Han, J., Huang, Y., et al. (2022) Lanthanum-Based Adsorbents for Phosphate Reutilization: Interference Factors, Adsorbent Regeneration, and Research Gaps. Sustainable Horizons, 1, Article 100011. https://doi.org/10.1016/j.horiz.2022.100011 |
| [39] | Thomé, A., de Souza, T.O., Thomé, G.C.H. and Reginatto, C. (2020) Phytotoxic Effect on Corn and Soybean Due Addition of Nanoiron to the Soil. Water, Air, & Soil Pollution, 231, Article No. 12. https://doi.org/10.1007/s11270-019-4384-6 |
